Silicone-hydrogel films are used to make extended wear soft contact lenses due to their high oxygen permeability, flexibility, comfort and reduced corneal complications. Conventional hydrogel materials (e.g. 2-hydroxyethylmethacrylate, HEMA) by themselves have poor oxygen permeability and they transport oxygen to the eye through the absorbed water molecules. Water has low oxygen permeability, also called the Dk value, which may be expressed in Barrer, wherein 1 Barrer=10−11 (cm3 O2) cm cm−2 s−1 mmHg−1 where ‘cm3 O2’ is at a quantity of oxygen at standard temperature and pressure and where ‘cm’ represents the thickness of the material and cm−2 is the reciprocal of the surface area of that material. The Dk of water is 80 Barrer. These lenses upon exposure to atmospheric air for longer periods are slowly dehydrated and the amount of oxygen transported to the cornea is reduced. Eye irritation, redness and other corneal complications can result and hence restrict use of the lenses to limited periods of wear.
Silicone-hydrogels with the comfort of soft contact lenses and significantly higher oxygen permeability overcame the obstacles for periods of wear beyond conventional hydrogels and were revolutionary in the field of optometry. The following patents describe silicone-hydrogels for use in contact lenses.
U.S. Pat. No. 4,260,725 to Bausch & Lomb Inc describes a water absorbing, soft, hydrophilic, flexible, hydrolytically stable, biologically inert contact lens with the capability of transporting oxygen sufficiently to meet the requirements of the human cornea comprising a polysiloxane which is α,ω terminally bonded through divalent hydrocarbon groups to polymerizably activated unsaturated groups and which contain hydrophilic sidechains.
U.S. Pat. No. 5,352,714 also to Bausch & Lomb Inc. describes silicone-containing hydrogels with enhanced wettability comprising a silicone-containing monomer, hydrophilic monomers, and a relatively non-polar ring-containing monomer able to be converted to a highly polar amino acid upon hydration.
U.S. Pat. No. 5,998,498 to Johnson & Johnson Vision Products describes a silicone hydrogel prepared by curing a reaction mixture comprising a silicone-containing monomer having the following structure:
wherein R51 is H or CH3, q is 1 or 2 and for each q, R52, R53 and R54 are independently ethyl, methyl, benzyl, phenyl or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units, p is 1 to 10, r=(3−q), X is 0 or NR55, where R55 is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1, and L is a divalent linking group which preferably comprises from 2 to 5 carbons, which may also optionally comprise ether or hydroxyl groups, for example, a polyethylene glycol chain.
U.S. Pat. No. 6,867,245 to Asahikasei Aime Co. describes a soft contact lens, and provides a contact lens which shows small and stable contact angle to water at its surface in water as well as in air, little deposition in wearing, high oxygen permeability, no adhesion of lens to a cornea and superior extended-wearing characteristics. It describes a hydrogel soft contact lens, which has contact angle at a lens surface in a range of 10-50° by the captive bubble method in water and 3 & 90° by the sessile drop method in air, oxygen permeability of not less than 30 and water content of not less than 5%, and also a hydrogel soft contact lens consisting of a polymer comprising a hydrophilic siloxanyl monomer shown by a specified general formula. This patent discloses copolymers of hydrophilic siloxane with amide-group containing monomers that are stated as being useful materials for contact lenses. The polymer comprises hydrophilic amide-group containing siloxanyl methacrylate, a siloxanyl methacrylate (tris[trimethylsiloxy] silylpropylmethacrylate, abbreviated as TRIS) including a hydrophilic polyether modified siloxanyl alkyl methacrylate and a crosslinkable monomer.
U.S. Pat. No. 6,013,711 to the CK Witco Corporation describes a method for improving the miscibility of the lower molecular weight unsaturated siloxane-polyether copolymers with the α,ω-divinylpolysiloxanes without loss of storage stability, or delay of cure at the vulcanization temperature, or loss of permanent hydrophilicity or other desirable features of the cured polysiloxane. The compositions comprise one or more α,ω-divinylpolysiloxanes, unsaturated polysiloxane-polyether copolymers having from 2 to 5 silicon atoms per molecule, which are preferably trisiloxanes, and a compatibilizing additive. The permanently hydrophilic, rapidly wettable polysiloxane compositions yield static water contact angles <50° and dynamic advancing contact angles of less than about 100.
U.S. Pat. No. 6,207,782 to Crompton Corporation discloses acrylated hydrophilic polysiloxanes monomers and polymers and their copolymers with acrylate/methacrylate comonomers and their emulsions for personal care, textile and coating applications. The acrylated siloxanes are represented by formula a[R3SiO1/2]m[O1/2SiR2O1/2]n[SiO3/2R]o[SiO4/2]p  (a)wherein R is selected from the R1 and P, wherein each R1 can be the same or different and each is a monovalent hydrocarbon group; each P is R3[O(CbH2bO)zCOCR4═CH2]g wherein, R3 is a polyvalent organic moiety, which may be hydroxy substituted alkylene, g is the valency of R3 minus 1, R4 is hydrogen or methyl; b=2 to 4, preferably 2 to 3; z=1 to 1000, preferably 3 to 30; and m+n+p+o=l to 100, preferably 2 to 20, at least one R is P; n=1 to 100; when o is not zero n/o <10:1; when p is not zero n/p <10:1; and m=0 to 10. A preferred acrylated siloxane of the invention is of the Formula (b)QR12Si[O—SiR12]x[O—SiR1P]yOsiR12Q  (b)wherein x, and y can be 0 or an integer, preferably each x and y are from 0 to 100, most preferably 0 to 25; Q can be R1 or P, with the proviso that the average acrylate functionality is >1 unsaturated groups per molecule. In the preferred embodiment y=0 and Q=P.
Conventionally, silicone-hydrogels are made by polymerizing the acrylate or methacrylate functionalized silicone monomer with hydrogel (hydrophilic) monomers, such as hydroxyethyl methacrylate (HEMA), N-Vinylpyrrolidone (NVP) and other monomers such as methyl methacrylic acid (MA), Dimethylacrylamide (DMA), etc, in the presence of crosslinker and free radical or photoinitiators. Crosslinking agents generally have two or more reactive functional groups at different sites of the molecule. Typically, these sites contain polymerizable ethylenic unsaturation groups. During curing, they form a covalent bond with two different polymer chains and form a stable three-dimensional network to improve the strength of the polymer. Crosslinking agents conventionally used in contact lenses include ethylene glycol dimethacrylate and trimethyloylpropane trimethacrylate (about 0.1 to 2 wt %). Other useful crosslinking agents include diethyleneglycol dimethacrylate, bisphenol A dimethacrylate, diglycidyl bisphenol A dimethacrylate and dimethacrylate-terminated polyethylene glycol and reactive linear polyether modified silicones.
Generally, silicone hydrogel contact lens materials are made using either hydrophobic mono-functional silicone monomer (such as TRIS) or multi-functional hydrophilic, silicone monomer followed by secondary surface treatment. Mono-functional silicone monomers are preferred in the contact lens industry over multi-functional silicone monomers since the latter lead to increased rigidity of the lens made therefrom.
Although the state of this art for soft contact lenses has been improving, the silicone-based materials described in these patents still possess major shortfalls, like sub-optimal surface wettability and lipid deposition. In an effort to overcome these drawbacks, current state of the art technology uses either expensive secondary surface treatments called ‘plasma oxidation’ or use internal wetting agents at the expense of oxygen permeability. Hence there remains a need for hydrophilic silicone monomers with inherently advantageous wettability and oxygen permeability that can be used to make contact lenses without the drawbacks and expensive surface treatments necessary with the silicone containing materials of the present art.
Hydrosilylation synthesis of siloxane-polyether copolymers with alkyl branched unsaturated polyethers, such as methylallyl polyethers, is known in the art. See for example, U.S. Pat. No. 3,507,923 and U.S. Pat. No. 4,150,048. However, the realization of improved oxygen permeability and water wettability in polymer films prepared from acrylate and methacrylate capped derivatives of these siloxane-polyether copolymers is novel. Accordingly, the present invention discloses new mono-acrylate or methacrylate functionalized silicone monomers containing a polyether moiety with a branched linking group, processes to produce such monomers with high purity and ease of manufacturability and homo and copolymers made from these monomers that have greater hydrophilic functionality. These functionalized silicone monomers are useful to make water-absorbing, oxygen-permeable silicone-hydrogel films that can be fashioned into extended wear soft contact lens. In particular, the monomers disclosed in the current invention have a branched linking group, which connects the siloxane unit with the polyalkyleneoxide block terminally functionalized with a reactive methacrylate group. Silicone hydrogel films produced with these monomers offer improved surface wettability, oxygen permeability and mechanical properties in comparison to silicone-hydrogel films prepared from monomers having linear alkyl linking groups, such as those already disclosed in the prior art for contact lens applications.